Process of producing alkyl benzene hydrocarbon sulfonates



. D. A.4 FEIL PROCESS oF PRoDucING .ALKYL BENZENE HYDROCARBON SULB/ONATES Filed Dec. 26,1` 1947 oct. 1o, 195o INVENTOR DeZma/", Fell BY c i Z @4M ATTORNEY Lima AMQlH f produce products Patented Oct. 1950 PROCESS OF PRODUCING ALKYL BENZENE HYDROCARBON SULFGNATES Delmar A. Feil,

Snyder, N. Y., assignor to Allied Chemical & Dye Corporaltion,

New York, N. Y.,

a corporation of New Yor Application December 26, 1947, Serial No. 793,862 10 Claims. (Cl. 2 60-505) 'I'his invention relates to improvements in the manufacture of detergents and related compositions comprising mixtures of sulfonated substituted derivatives of a benzene hydrocarbon such as benzene, toluene, etc., in which the substituent groups are derived from a poly-component nonaromatic hydrocarbon mixture as, for example, a distillate of crude petroleum or synthetic mixtures such as Fischer-Tropsch fractions or synthetic olens. Preferably the substituent groups are derived from a kerosene fraction of a petroleum distillate. The invention is an improvement on the invention disclosed and -claimed in U. S. Patent 2,340,654 granted February 1, 1944.

U. S. Patent 2,340,654 discloses the condensation of a benzene hydrocarbon with a chlorinated kerosene fraction in the presence of aluminum chloride or other Friedel and Crafts condensing agent and allowing the resultant reaction mixture to stand so as to form an upper oily layer containing a crude so-called alkyl benzene condensation product and a lower layer of tar or sludge containing the residual and exhausted condensation agent. The upper layer is withdrawn, distilled to remove unreacted benzene hydrocarbons and other low-boiling constituents and thereafter further distilled under reduced pressure to remove as distillate the desired so-called alkyl benzene compounds. As disclosed in this patent, the further distillation is carried out carefully to leave a distillation residue sation product subjected to the further distillation to avoid introducing into the distillate higher condensation products which on sulfonation which interfere with the detergent action of the alkyl benzene sulfonates. Actually, in the commer-cial practice of the process of Patent 2,340,654 it is generally customary to leave as distillation residue from about 12% to about 15% of the condensation product subjected to the further distillation to produce a product which upon sulfonation conformswith the quality standards demanded of the ultimate detergent product. These large amounts of distillation residues represent large losses of the ultimate detergent product, which losses have heretofore been considered unavoidable in order to produce a detergent product of desired high quality.

of at least 10% of the conden- It is an object of this invention to provide a l novel process for producing mixed alkyl benzene sulfonates from complex mixtures of non-aromatic hydrocarbons and a benzene hydrocarbon in materially' greater yield than is produced by the process hereinabove described and this without sacrifice of quality of the ultimate detergent product.

Other objects and advantages of the invention will be apparent from the following detailed description thereof.

Surprisingly, I have found that materially greater yields of refined alkyl benzene condensation product result, which product upon sulfonation produces a detergent of at least equal quality to that heretofore produced by subjecting the upper oily layer containing the crude alkyl benzene condensation product to distillation to separate substantially al1 of the unreacted benzene and most of the other low-boiling constituents, thereafter continuously introducing the residual material into a zone wherein this material is rapidly converted to an attenuated form, this zone being maintained at an absolute pressure not exceeding about 20 mm. of mercury and preferably heated to a temperature such that the vapors leaving this zone are at a temperature of from 190 to 250 C. and continuously removing the vapor and residue from this zone, the residual material being introduced at a rate such that the average time of sojourn of the vapors formed in this zone does not exceed 5 minutes, preferably not in excess of 1 minute. Thus, by treating the oily layer containing the crude alkyl benzene condensation product as hereinabove described, as much as or more of the material subjected to treatment may be recovered as refined condensation product, which when sulfonated produces a s'ulfonated detergent at least equal in quality to that produced by the process of said Patent 2,340,654 in which 90% or less of the material subjected to the aforesaid further distillation is sulfonated. Hence, the process of this invention results in an increase in yield of at least 5%, usually about 8% to 10%.

Within the ranges of pressure and temperature above given lower pressures should be used with correspondingly lower temperatures'. Temperatures as high as 250C. may be used with higher pressures Within the pressure range above given. The use of a maximum temperature with a minimum pressure within the ranges above given should be avoided because of the danger of distilling high-boiling color-forming and other harmful constituents. ,A

As the poly-component non-aromatic hydrocarbon mixture, a petroleum distillate containing not more than 20 a of `aromatic compounds and boiling within the kerosene range is preferred, i. e., petroleum distillates boiling within the range of 180 to 320 C. Those which boil for the most part (i. e., at least 80% thereof) within the range of 210 to 320 C. are particularly preferred, especially when composed predominantly of aliphatic and/oralicycllc hydrocarbons which boil within. the range of 210 to 290 C. The substituent groups derived fro-m these hydrocarbon mixtures and other mixtures such as synthetic oleflns which may be used and thus introduced into the benzene nucleus of a benzene hydrocarbon to form a mixture of substituted benzenes are principally hydrocarbon groups. which may be also isomeric and homologous in character. The alkyl groups contain at least carbon atoms per hydrocarbon molecule, usually from 10 to 20 carbon atoms per molecule. The substituent groups may include straight chain and branched chain alkyl groups, aralkyl and cycloalkyl groups and chlorinated forms of these groups. all of which are included herein in the term alky vIn general, the manufacture of the composition in accordance with this invention involves condensing a benzene hydrocarbon such as benzene, toluene, etc., with a halogenated hydrocarbon mixture such as a petroleum fraction or an oleiinic product, for example, one obtained by removing hydrogen halide from a halogenated mixture of hydrocarbons, separating the oily layer containing the crude alkyl benzene compound from the tar or sludge, distilling the oily layer to separate substantially all of the unreacted benzene hydrocarbons and most of the other lowboiling constituents, and thereafter continuously introducing the residual material into a zone wherein it is rapidly converted to an attenuated form. The zone is maintained at an absolute pressure not exceeding about mm. of mercury, preferably not exceeding about 5 mm of mercury, and is preferably heated to a temperature such that the resulting vapors leave this zone at a temperature of from 190 to 250 C. This residual material is introduced into this zone at a rate such that the average time of sojourn of the vapors formed in this zone does not exceed 5 minutes, preferably not in excess of l minute. The resulting vapors are continuously withdrawn from this zone, condensed, and the mixture of refined alkyl benzene condensation products thus produced sulfonated.

In accordance with a preferred embodiment of the present invention, a selected. distillate fraction of a poly-component non-aromatic hy- -drocarbon mixture, for example, a kerosene fraction of Pennsylvania or similar petroleum boiling mainly over a maximum range less than 100 C. in'extent, and especially one which boils within the range of about 175 C. lto 275 C., is chlorinated to obtain a mixture which comprises by-products of the condensation. The separation treatment preferably involves permitting the condensation reaction mixture to stand undisturbed so as to stratify into an upper oily layer containing the crude alkyl benzene condensation product and a lower layer of sludge, followed by separation of the layers, as by deeantation. The upper oily layer is thereafter subjected to distillation to remove as distillate low-boiling constituents such as unreacted benzene, kerosene and chlorinated hydrocarbons.

, This distillation is continued until the aniline point of the distillant does not exceed about C. Thereafter this distillation is discontinued and the residual material is continuously passed through a preheater Whereit is rapidly heated in the liquid state to a temperature not exceeding about 250 C. and then at this temperature the preheated liquid is introduced into a heated zone in which it is immediately converted to an attenuated form. The heated zone is maintained under an absolute pressure not exceeding about 20 mm. of mercury, Preferably not exceeding about 5 mm. of mercury and at a temperature such that the vapors leave the zone at a temperature of from 190 to 250 C., preferably 200 to 225 C. The rate of introduction of the preheated liquid is such that the vapors chlorinated hydrocarbons. The kerosene desiru ably is chlorinated to an extent corresponding with from ,'15 to 200 percent mono-chlorination, i. e., chlorination to an extent such that the resulting chlorinated kerosene contains the amount of organically combined chlorine which would be present if three-fourths to two atoms of chlorine were introduced into each molecule of hydrocarbon present in the original kerosene. The mixture of chlorinated hydrocarbons is condensed with a benzene hydrocarbon in the presence of aluminum chloride as a catalyst or condensing agent (or other Friedel and Crafts condensing agent) in amount desirably less than 9 percent, preferably about 5 percent or less, of the weight of the chlorinated kerosene. The resulting condensation reaction mixture is then subjected to a mechanical separation treatment to separate a crude mixture of alkyl benzene compounds from a tarry sludge containing the reproduced therefrom have an average time of sojourn in this zone not exceeding flve minutes, preferably not exceeding one minute.

The vapors are condensed and the condensate is sulfonated. sulfuric acids of various strengths such as 99 to 100 percent sulfuric acid, 26 percent oleum and 65 percent oleum, or chlorsulfonic acid may be used as sulfonating agents. The sulfonation may be carried out in the presence of inert solvents or diluents, and sulfonation assistants, as, for example, the lower fatty acids and their anhydrides, such as acetic acid and acetic anhydride, or the alkali metal sulfates, such as sodium or potassium sulfate, may be employed. Also, the temperature at which the sulfonation is carried out maylvary within vwide limits. For example, temperatures as low as about 20 C. and as high as about 140 C. may be employed. In general, the more vigorous the sulfonating agent the lower is the preferred temperature. In most cases the sulfonation is carried out most eillciently at temperatures between 5 and 100 C. For complete sulfonation the sulfonating agent in terms of 100 percent sulfuric acid may be employed in amounts which range from 0.3 to 5 times or more of the vcondensation product to be sulfonated. Ordinarily, the extent to which the sulfonation is carried out will vary with the individual material being sulfonated, the duration of the sulfonation, and the use to be made of the sulfonated product.

The distillation or stripping of the upper oily layer to remove low-boiling constituents may be e'ected in any desired manner including the procedure described in pending patent application Serial No. 510,668 filed November 17, 1943 involving the continuous flow of the oily layer in contact with a surface heated to a temperature of at least 100 C. and below the boiling point of the mixture of alkyl benzenes present in the oily layer. As noted above, the stripping is continued until the distilland has an aniline point not exceeding about 30 C. in the case of alkyl benzene condensation products in which the alkyl groups are derived from the kerosenes disclosed in the sidual and/or exhausted condensing agent and examples. For condensation products made from from the sulfonation mass the stripping may be considered complete.

As above indicated; the crude alkyl benzene condensation product is preferably preheated in liquid 4state prior' to its introduction into the heated zone so as to reduce the amount of heat which must be furnished by the heated zone to vaporize the condensation product and thereby increase the vaporization capacity of the heated zone and promote more rapid and complete vaporization of the crude condensation product. The crude condensation product can be preheated in the liquid state to or above the temperature at which it will be vaporized at the reduced pressure within the heated zone and then introduced into the heated zone maintained at a sufficiently reduced pressure, e. g., below 20 mm. of mercury absolute, whereby the condensation product is ilashed into vapors, the latent heat of vaporization being supplied in part or completely by the sensible heat of the liquid. The preheating should be done rapidly to minimize the harmful results of exposure of the condensation product to elevated temperatures.

The average time of sojourn of the vapors formed in the heated zone may readily be calculated as the quotient of the volume of the heated zone divided by the volume of vapors generated and passed through this zone per unit time. By attenuated form is meant that the material is in atomized or spray form so that a relatively large surface of the material is subjected to the temperature conditions within the zone.

The accompanying drawing is a flow sheet illustrating this invention. It will be understood this invention is not limited to the particular types of units of equipment and arrangement thereof disclosed in this drawing.

As indicated in the drawing, benzene and chlorinated kerosene are condensed in reaction kettle I0. The condensation product flows, from this kettle through line II into decanter I2 where upon standing it stratifies into two layers. The lower tar layer is withdrawn through line I3. The upper oilylayer containing the crude alkyl benzene condensation product is discharged through line I4 into still I5 which may be of any well known type. Low-boiling constituents such as unreacted benzene, kerosene and chlorinated kerosene are taken off overhead from still I5 through line I6 which may lead to a condenser not shown. Uponremoval of these low-boiling constituents, the residual material comprising the crude kerosene-benzene condensation product is pumped continuously by pump I1 through line I8 into and through preheater I9.

Preheated material ows through line 20 on to the rotating conical distributor 2| disposed within the heated zone l22 consisting of a chamber 23 provided with a heating jacket 24 through which a suitable heating medium such as a mixture of biphenyl and diphenyl oxide is circulated. The liquid material continuously flowed on to the conical distributor 2| is thrown oi in the form of a film or spray. Appreciable vaporization occurs as the liquid enters the heated zone 22 and travels as a spray or film toward the heated wall of the chamber 23. On contact with the heated wall which it strikes near the top of the jacketed area further vaporization' of the remaining liquid occurs. Residual liquid flows down the wall of the chamber and along a spiral passage deiined by a helical baille 25 disposed on the base of the chamber; further vaporization occurs during this flow of the residual liquid. The residue reaches and flows out through conduit 26.

The vapors thus produced leave heated zone 22 through a line 21 passing to a condenser 28. The condensate produced in condenser 28 flows through line 29 towards a sulfonator 30.

The invention will be illustrated by the following examples, but it should be understood that the invention is not limited to them. In these examples the parts are by weight and the temperatures are in degrees centigrade.

Example I 15,320 lbs. of kerosene, of which the major portion was fresh Pennsylvania kerosene, which had a boiling range from 190 C. to 255 C., a specific gravity of 0.786 at 24 C., a content of 12 to 13% of aromatics and unsaturates, an aniline point of 71.6 C., and the minor portion was kerosene recovered from a previous condensation such as is described in this example, was chlorinated directly at about '70 C. with gaseous chlorine until u the specific gravity of the chlorinated mixture was 0.917 at 24 C.

333 lbs. of crushed anhydrous aluminum chloride was added to an agitated charge of 14,060 lbs. of benzene made up of a major portion of benzene recovered from a previous condensation such as is described in this example, and fresh benzene and the mixture was heated to 40 C. 7400 lbs. of the chlorinated kerosene was added during about 11/2 hours, the last half of the chlorinated kerosene being charged while heating the reaction mixture so that the temperature reached 50 C. at the conclusion of the addition. The reaction mixture was heated at 50 C. with agitation for an additional half-hour, and pumped to a settling tank and allowed to stratify for 11/2 hours into an upper oily layer and a lower tarry layer. The lower tarry layer, comprising the aluminum chloride residue resulting from the condensation and by-products, was withdrawn. The upper oily layer, comprising the desired kerosene-benzene condensation product (herein referred to as alkyl benzene) together with unreacted benzene, unchlorinated and chlorinated hydrocarbons and by-products of the chlorination and condensation, was pumped under atmospheric pressure through a flash vaporizer, wherein the material was rapidly heated to o C., causing substantially all of the benzene contained therein to be recovered by distillation, as described in U. S, Patent applicationI Serial No. 510,668, Process of Producing Alkyl Aryl Sulfonates, now Patent No. 2 441,351. The stripped oil was then distilled under an absolute pressure of about 10 in. of mercury until the aniline point of the distillate rose to 50 C. The distillates thus obtained were collected as "recovered benzene. The distillant was then further distilled under an absolute pressure of 1 to 2 in. of mercury until the aniline point of the still contents dropped to 25.5-26 C. The resulting distillate containing kerosene and unreacted chlorinated kerosene removed from the condensation product is used as recovered kerosene.

The residual material was then pumped through a preheater and into a heating zone similar to zone 22, shown on the drawing having a diam- 75 eter of 8' 6" and a vertical wall height of 3'.

The stream of crude alkyl benzene condensation compound in flowing through the preheater was heated to about 190 C. under atmospheric pressure, and was ilowed at a substantially uniiorm rate or 2323 pounds per hour into the heated zone which was evacuated to an absolute pressure of 6 mm. oi mercury and whose wall and bottom were heated to approximately 250 C. by vapors of biphenyl and diphenyl oxide circulated through the heating jacket. The liquid stream entering the heated zone was distributed and thrown out as a spray or lm toward the wall and was appreciably vaporized as it entered the heated zone and traveled toward the wall, Upon contact with the heated wall the liquid was further vaporized, the residual liquid flowing down the wall and along the spiral path on the bottom of the heated zone during which additional vaporization occurred; and nally flowing out through the outlet at the bottom of the heatedzone. The average time of sojourn of the vapors within the heated zone was about 1.2 seconds. The vapors left the heated zone at a temperature of 225 C., this temperature being maintained constant by automatic adjustment ofthe rate of flow of the heating medium in the jacket surrounding the heated zone, and were condensed and collected in a suitable receiver. 2190 pounds of distillate were thus obtained per hour, corresponding to a 94.3% recovery of the material introduced into the heated zone. 133 pounds of residue were obtained per hour, corresponding to 5.7% of the condensation product introduced into the heated zone.

The refined alkyl benzene condensation product thus obtained was purified by mixing it with approximately 18% by weight of 100% sulfuric acid and agitating the mixture for minutes at in an enamel kettle. The mixture lwas allowed to stand for 30 minutes and the resulting lower layer, comprising acids and impurities, was withdrawn and discarded. The upper layer of acid treated material was sulfonated by mixing it with 1.4 parts of 100% sulfuric acid and heating the mixture with agitation to -60 C. for one hour. The sulfonation mixture was neutralized with aqueous caustic soda and sufilcient sodium sulfate was then added to adjust the inorganic salt content in the mixture to approximately of the total solute in the solution.

The resulting slurry was mixed thoroughly and dried on a double rotary drum drier.

For purposes of comparison, a portion of the same condensation product which was introduced into the heated zone was subjected to batch disl tillation under an absolute pressure of 5 mm. of

mercury and the distillate was collected separately until the boiling point of the distillate reached 235 C. Only a 90% recovery of alkyl benzene condensation product was obtained. This condensation product, when purified and sulfonated in the same manner as hereinabove described, resulted in the production of 227 parts of detergent product containing 90.8 parts of organic sulfonate free from inorganic salts per 100 parts of crude alkyl benzene subjected to the aforesaid batch distillation. In the practice of the present invention 240.3 parts of detergent product, containing 96.1 parts of organ-ic sulfonate free from inorganic salts, and of at least equal quality were produced per 100 parts of crude alkyl benzene introduced into the heated zone. Hence, the above comparison demonstrates an `improvement of 5.8% in yield of detergent.

Example I! In this example the amount of aluminum chloride employed in the condensation was 7% of the weight of the chlorinated kerosene instead of 4.5% by weight used in Example I; otherwise the initial portion of the example was the same as in Example I. 'Ihe oily layer containing alkyl benzene condensation product after distillation of unreacted benzene, kerosene and chlorinated kerosene therefrom was pumped uniformly at the rate of 1972 pounds per hour ,through a preheater where it was heated to 190 C. under atmospheric pressure and then into a. heated zone of the same type as used in Example I and the walls of which were heated to a temperature 0f about 250 by means of biphenyl and diphenyl oxide vapors circulated through the jacket. This heated zone was evacuated to an absolute pressure of 6 mm. of mercury. Vapors of refined alkyl benzene condensation product were withdrawn from the heated zone at a temperature of 205 at a rate of 1907 pounds per hour and were totally condensed in a suitable condenser and collected in a receiver. The residue drained continuously from the heated zone from the bottom outlet to a receiver at a rate of 65 pounds per hour, corresponding to 3.3% by Weight of material introduced hourly into the heated zone. The average time of sojourn of the vapors within the heated zone was 1.5 seconds. The alkyl benzene was purified and sulfonated following the same procedure as described in Example I.

For comparative purposes material identical with that introduced into the heated zone was subjected to batch distillation, as described in connection with Example I, to recover the alkyl benzene condensation product, which was thereafter purified and sulfonated following the same technique as employed in Example I. The detergent product produced by the procedure of this invention and that produced for comparative purposes possessed the same color in a 5% aqueous solution, and the former Was the equal or superior in detergent, foaming and solubility properties. Whereas the batch distillation method employed for purposes of comparison resulted in the production of parts refined alkyl benzene condensation product and 229.5 parts of detergent product containing 91.8 parts of organic sulfonate free from inorganic salts per parts of material subjected to distillation, the process of this invention resulted in 96.7 parts of refined alkyl benzene condensation product and 257.5 parts of detergent product containing 103 parts of organic sulfonate free from inorganic salts per 100 parts of alkyl benzene condensation product introduced into the heated zone. This example. therefore, demonstrates an improvement of 12.2% in yield of detergent.

Elample II In this example, a Pennsylvania kerosene boiling from C. to 275 C., possessing a speciiic gravity of 0.785 at 24 C., an aniline point of 72 C. and containing 14 to 15% of aromatics and unsaturates, and 5% of aluminum chloride based on the weight of chlorinated kerosene were used in effecting the condensation of the benzene and chlorinated kerosene; otherwise, the initial portion of the example was the same as the initial portion of Example I. The oily layer containing the alkyl benzene condensation product, after distillation to remove unreacted benzene, kerosene and chlorinated kerosene, was pumped at the uniform rate of 25.5 pounds per hour through a preheater where it was heated to a temperature .of 160 C. under atmospheric pressure and thence into a. heated zone, which was evacuated to an absolute pressure of 4-mm. of mercury, and the walls of which were heated to 250 C. by a mixture of biphenyl and diphenyl oxide circulating through the heating jacket. The heated zone used was 2 in diameter and 2' high and did not contain a distributor corre` sponding to distributor 2| of the drawing but ywas provided with a. helical baflle at its bottom fov ming a spiral path over the dished base of the hey ted zone. The condensation product was introduced through a tangentialinlet into the start of the spiral path at the top of the base of the heatedzone, and flowed along the spiral path, during which ilow the liquid was rapidly vaporized. The average time of sojourn ofl the vapors within the heated zone was approximately 2.9 seconds. The exit vapors were totally condensed, and the liquid residue was collected continuously in a suitable receiver. The temperature of the vapors leaving the heated zone was maintained at about 224 C. by suitable adjustment of the rate of flow of the biphenyl and diphenyl oxide through the jacket. The resulting distillate containing the refined alkyl benzene condensation product was purified and sulfonated in the same manner as in the preceding examples.

For comparative purposes, material identical with that introduced into the heated zone was subjected to batch distillation, as described above, to recoverthe alkyl benzene condersation product as distillate, which was thereafter puriiled and sulfonated employing the same technique as thatidescribed in Example I. For each 100 pounds of alkyl benzene condensation product introduced into the heated zone 93.7 pounds of refined alkyl benzene condensation product were obtained, which yielded 276 parts of detergent product containing 110.4 parts of organic sulfonate free from inorganic salts. In the comparative example, for each 100 parts of material subjected to batch distillation 86.5 parts of puried alkyl benzene were obtained, which yielded 251.8 parts of detergent product containing 100.7 parts of organic sulfonate free from inorganic salts. The quality of'the detergent produced by this example of the present invention was at least as good as that obtained in the comparative procedure. Accordingly, this example demonstrates an improvement of 9.6% in yield of detergent.

It will be evident that the invention is not limited to the details of the foregoing illustrative examples and that changes can be made without departing from the scope of the invention. Thus the nature of the poly-component non-aromatic hydrocarbon mixture employed, the manner and degree of chlorination or other treatment to which it is subjected prior to condensation with the benzene hydrocarbon, and the conditions of condensation may be varied. Further, the proportion of benzene hydrocarbon compound employed can be varied. Generally, the amount of benzene hydrocarbon to be employed is dependent upon the amount of combined chlorine contained in the chlorinated hydrocarbon mixture. In order to obtain complete reaction, one mol of benzene hydrocarbon should be used for each atom of combined chlorine in the chlorinated hydrocarbon mixture. Preferably, an excess of the benzene hydrocarbon is used as this favors complete reaction of the chlorinated hydrocarbon.

It will be noted that this invention results in a materially greater yield of alkyl benzene sulfonate than is produced by prior processes, and this without sacrifice of quality of the ultimate detergent product. The improvement in yield is obtained by ehecting the vaporization of the alkyl benzene condensation product under the particular conditions hereinabove described so as` to reduce materially the amount or' residue discarded. Taking into account the teachings of the prior art that ln order to produce a detergent product of satisfactory quality it is important to carry out the distillation of crude alkyl benzene condensation product so as to leave a residue consisting of at least 10% of the material subjected to such distillation, and that this residue consists substantially entirely of polyalkyl benzene condensation products and polyaryl alkyl condensation products, which, when sulionatd, have a deleterious eiect upon the detergent properties of the ultimate detergent product, it is indeed unexpected and surprising that by observing the conditions of this invention 9o/0 or more of the crude alkyl benzene condensation product can be recovered and sulfonated to produce a product of desired high quality.

By the term poly-component non-aromatic hydrocarbon mixture is meant a hydrocarbon mixture, such as petroleum and petroleum distlllates or otherwise rened petroleum fractions, containing straight and/or branched chain alkanes or alkenes, and which may also contain cycloalkanes and aromatic hydrocarbons but does not contain more than 20 percent of aromatic hydrocarbons.

What is claimed is:

1. A process or producing alkyl benzene sulfonates adapted for use as a detergent, which comprises forming a benzene hydrocarbon condensation product of a poly-component non-aromatic hydrocarbon mixture, stratifying the resulting'condensation reaction mixture into an oily layer comprising the crude alkyl benzene compounds and a sludge-like layer containing other constituents, distilling the oily layer to remove unreacted benzene hydrocarbons and other lowboiling constituents therefrom, continuously passing the residual product from the aforesaid distillation step into a heated zone maintained at an absolute pressure not exceeding about 20 mm. of mercury and at a rate such that the average time of sojourn of the vapors formed in this zone within this zone does not exceed ve minutes, continuously removing and condensing the vapors of alkyl benzene hydrocarbon condensation products leaving this zone and sul-v fonating the benzene hydrocarbon compounds thus produced.

2. In the process of producing alkyl benzene sulfonates adapted for use as a detergent by forming a benzene hydrocarbon condensation product of a poly-component non-aromatic hydrocarbon mixture, stratifying the resulting condensation reaction mixture into an oily layer comprising the crude alkyl benzene compounds and a sludge-like layer containing other constituents, distilling the oily layer to remove unreacted benzene hydrocarbons and other lowboiling constituents therefrom, the improvement which comprises continuously passing the residual product from the aforesaid distillation step into a heated zone maintained at an absolute.7

pressure not exceeding about 20 mm. of mercury heated to a temperature such that the vapors leaving this zone are within the range of to acetate 250 C. and at a rate such that the average time of sojourn of the vapo'rs formed in this zone within this zone does not exceed five minutes, the residual product upon introduction being rapidly converted to an attenuated form, and continuously removing and condensing the vapors leaving this zone.

3. A process of producing alkyl benzene sulfonates adapted for use as a detergent, which comprises forming a benzene condensation product of aY kerosene fraction, stratifying the resulting. condensation reaction mixture into an.

oily layer comprising the lcrude alkyl benzene compounds and a sludge-like layer containing other constituents, distilling the oily layer to remove unreactedvbenzene and other low-boiling constituents therefrom, continuously passing the residual product from the aforesaid distillation step into a heated zone maintained at an absolute pressure not exceeding about 20 of mercury heated to a temperature such that the vapors leaving this zoneare within the range of 190 to 250 C. and at a rate such that the average time of sojourn of the vapors formed in this zone within this zone does not exceed five minutes, continuously removing and condensing the vapors leaving this zone, the vapors thus condensed constituting at least 95% by weight of the said residual product introduced into said heated zone, and suli'onating the alkyl benzene condensation compounds thus produced.

4. A method of producingalkyl benzene sulcomprises condensing a benzene hydrocarbon with one of the group consisting of a halogenated kerosene fraction of petroleum distillate and olens derived therefrom in the presence of a condensing agent, stratifying the resulting reaction mixture intoan oily upper layer containing alkyl benzene hydrocarbon compounds and a lower layercontaining the condensing agent, subjecting the oily layer to distillation to remove therelrom unreacted benzene hydrocarbons xand other low-boiling constituents, con-J tinuously flowing the residual material from the aforesaid distillation treatmenty into a heated zone maintained at an absolute pres' sure not exceeding about 20 mm. of mercury heated to a temperature such that the vapors leaving this zone are within-therange of 190 to 250 C. and at a rate such that the average time of sojourn of the vapors formed in this zone within this zone does not exceed one minute, the residual material upon introduction into the heated zone being converted to a form which exposes a large surface of the material to temperature conditions within the heated zone, continuously removing and condensing the vapors `of alkyl benzene hydrocarbon condensation compounds leaving this zone and sulfonating the re-v fined alkyl benzene hydrocarbon condensation compounds thus produced.

5. A method of producing alkyl benzene sulfonates adapted for use as a detergent, which comprises condensing benzene with one of the group consisting of a halogenated kerosene fraction of petroleum distillate and olens derived therefrom in the presence of aluminum chloride, stratifying the resulting reaction mixture into an oily upper layer containing alkyl benzene compounds and a lower layer containing the aluminum chloride and by-products of the condensation, subjecting the oily layer to distillation to remove therefrom unreacted benzene, continuously flowing the residual material from the aforesaid distillation treatment into a heated zone wherein it is iinmediateiy converted to an attenuated form, said zone being maintained,

at an absolute pressure not exceeding about zu mm. of mercury and heated to a temperature such that the vapors leaving this zone are within the range or' 190 to 250 C. and said material being introduced at a rate such that the average time of soJourn of the vapors formed in this .zone within this zone does not exceed about one minute, continuously removing and condensing the vapors oi alkyl benzene condensation compound leaving this zone and sulionating the renned alkyl benzene condensation compounds thus produced.

6. A method /of producing alkyl -benzene sulfonates adapted for use as a detergent, which comprises condensing benzene with one of the group consisting of4 a halogenated kerosene fraction of petroleum distillate and olenns derived therefrom in the presence of aluminum chloride, stratiiying the resulting reaction' mixture into an oily upper layer containing alkyl benzene compounds and a lower layer containing the aluminum chloride and by-products of the condensation, subjecting the oily layer to distillation to remove therefrom unreacted benzene, continuously preheating the residual material 'from the aforesaid distillation treatment to a,

temperature not exceeding 250 C., continuously introducing the preheated material into a heated zone wherein the material is immediately converted into attenuated form, said zone being maintained at an absolute pressure not exceeding about 5 mm. of mercury and heated to a temperature such that the lvapors leaving this zone are within the range of 200 to 225 C. and said material being introduced at a rate such that the average time ofsojourn of the vapors formed in this zone Within this zone does not exceed about one minute, continuously removing and condensing the vapors of alkyl benzene Ycondensation compounds leaving this zone and suifonating the rened alkyl benzene condensation compounds thus produced.

'7. A method of producing higher alkyl benzene sulfonates adapted for use as a detergent which comprises reacting benzene with a chlorinated kerosene fraction of a petroleum distillate of the Pennsylvania type boiling mainly over a maximum range less than C. in extent, which has been chlorinated to an extent corresponding with from 75 percent to 200 percent chlorination, with the aid of anhydrous aluminum chloride in an amount less than 9 percent of the weight of the chlorinated kerosene, the amount of benzene employed being in excess of one mol per atom of combined chlorine in the chlorinated kerose stratifying the resulting condensation reacti` mixture into an upper oily layer containing alk, benzenes and a lower layer containing the aluminum chloride sludge and by-products of the condensation, separating the layers, removing residual benzene and other low-boilingcomstituents. from the oily layer by distillation, preheating the residual material to a temperature not exceeding about 250 C., continuously ini troducing the preheated material into a heated and condensing the vapors of alkyl benzene condensation compounds leaving this zone and sulfonating the reiined alkyl benzene condensation compounds thus produced.

8. A method of producing alkyl benzene sulfonates adapted for use as a detergent which comprises reacting benzene with a chlorinated kerosene fraction of a petroleum distillate of the Pennsylvania type vboiling mainly over a maximum range less than 100 C. in extent. which has been chlorinated to an extent corresponding with from 75 percent to 200 percent chlorination, with the aid of anhydrous aluminum chloride in an amount about percent of the weight of the chlorinated kerosene, the amount of benzene employed being in excess of one ymol per atom of combined chlorine in the chlorinated kerosene, stratifying the resulting condensation reaction mixture into an upper 'oily layer containing alkyl benzenes and a lower layer containing the aluminum chloride sludge and byproducts of the condensation, separating the layers, distilling the oily layer to remove residual benzene and other low-boiling constituents, said distillation being continued until 'the dlstilland has an aniline point not exceeding about 30 C., preheating the residual material to a temperature not exceeding about 250 C., continuously introducing the preheated material into a heated zone wherein the material is immediately converted to an attenuated form, said zone being maintained at a pressure not exceeding about 5 mm. of mercury absolute and at a temperature such that the vapors leaving this zone are within the range of 200 to 225 C., said material being introduced at a rate such that the average time of sojourn of the vapors formed in this zone within this zone does not exceed about one minute, continuously removing and condensing the vapors of alkyl benzene condensation compounds leaving this zone, the vapors thus condensed constituting at least 95% by weight of the said preheated material introduced into the said heated zone, and sulfonating the refined alkyl benzene condensation compounds thus pro duced.

9. In the process of producing alkyl benzene sulfonates adapted to be used as detergents by formingy "a benzene hydrocarbon condensation product with a poly component, non-aromatic 5, 2,316,670' hydrocarbon mixture, stratifying the resulting' condensation reaction mixture into an oily layer comprising the crude alkyl benzene hydrocarbon compounds and a sludge-like layer containing other constituents, distilling the oily layer to remove unreacted benzene hydrocarbons .and other low boiling constituents therefrom, the improvement which comprises continuously introducing the' residual product from the aforesaid distillation step into a heated zone wherein the product is immediately converted to an attenuated form, said zone being maintained at a pressure within the range of from 0 to 20 mm. of mercury absolute and at a temperature such that the vapors leaving said zone are within the range of 190 to 250 C., the pressure and temperature at which said zone is maintained within said ranges being correlated so that when said zone is maintained at a lower pressure within said pressure range it is also maintained at a lower temperature within said temperature range and when maintained at-a higher pressure within said pressure range it is also maintained at a higher temperature within said temperature range, said residual product being introduced at a rate such that the average time of sojourn of said vapors formed in said zone within said zone does not exceed about flve minutes, continuously removing and condensing the vapors leaving said zone, the vapors leaving said zone constituting at least by weight of the said residual product introduced into said zone, and sulfonating the alkyl benzene hydrocarbon condensation compounds thus produced.

10. A process as dened in claim 9, in which the said zone is maintained at the pressure within the range of from 0 to 5 mm. of mercury absol-ute and at a temperature such that the vapors leaving said zone are within the range of 200 to 225 C. and the residual material is introduced at a rate such that the average time of sojourn of vapors formed in said zone within said zone 'lhe following references are of record inthe file of this patent:

UNITED STATES PATENTS Number Name Date `Colgate et al Apr. 13, 1943 2,340,654

Flett Feb. 1, 1944- 

1. A PROCESS OF PRODUCING ALKYL BENZENE SULFONATES ADAPTED FOR USE AS A DETERGENT, WHICH COMPRISES FORMING A BENZENE HYDROCARBON CONDENSATION PRODUCT OF A POLY-COMPONENT NON-AROMATIC HYDROCARBON MIXTURE, STRATIFYING THE RESULTING CONDENSATION REACTION MIXTURE INTO AN OILY LAYER COMPRISING THE CRUDE ALKYL BENZENE COMPOUNDS AND A SLUDGE-LIKE LAYER CONTAINING OTHER CONSTITUENTS, DISTILLING THE OILY LAYER TO REMOVE UNREACTED BENZENE HYDROCARBONS AND OTHER LOWBOILING CONSTITUENTS THEREFROM, CONTINUOUSLY PASSING THE RESIDUAL PRODUCT FROM THE AFORESAID DISTILLATION STEP INTO A HEATED ZONE MAINTAINED AT AN ABSOLUTE PRESSURE NOT EXCEEDING ABOUT 20 MM. OF MERCURY AND AT A RATE SUCH THAT THE AVERAGE TIME OF SOJOURN OF THE VAPORS FORMED IN THIS ZONE WITHIN THIS ZONE DOES NOT EXCEED FIVE MINUTES, CONTINUOUSLY REMOVING AND CONDENSING THE VAPORS OF ALKYL BENZENE HYDROCARBON CONDENSATION PRODUCTS LEAVING THIS ZONE AND SULFONATING THE BENZENE HYDROCARBON COMPOUNDS THUS PRODUCED. 